Reactive anthraquinone dyestuffs containing a tolylsulfonylmethylene oxytriazine group

ABSTRACT

REACTIVE TRIAZINE DYESTUFFS HAVING THE FORMULA:   CH3-(1,4-PHENYLENE)-SO2-CH2-O-(4-CL-1,3,5-TRIAZIN-2,4-YLEN   NH-CHROMOGEN-(-SO3H)N   WHEREIN CHROMOGEN IS AN ANTRAQUINONE DYESTUFF RESIDUE AND N IS AN INTEGER FROM 1 TO 4, AND PARTICULARLY EFFECTIVE FOR DYEING CELLULOSE. THE DYESTUFFS MAY BE ABSORBED AND FIXED ONTO THE CELLULOSE FIBERS BY HOT OR COLD DYEING TECHNIQUES. THE DYETSUFFS HAVE HIGH REACTIVITY AND GOOD DYEING POWDER AND THE DYEINGS OBTAINED THEREFROM HAVE HIGH BRILLIANCE AND PURITY OF CHROMATIC SHADES AND IMPROVED FASTNESS TO WASHING.

United States Patent Office Int. Cl. C07d 55/46 U.S. Cl. 260-249 2 Claims ABSTRACT OF THE DISCLOSURE Reactive triazine dyestuffs having the formula:

wherein chromogen is an anthraquinone dyestuff residue and n is an integer from 1 to 4, are particularly effective for dyeing cellulose. The dyestuffs may be absorbed and fixed onto the cellulose fibers by hot or cold dyeing techniques. The dyestuffs have high reactivity and good dyeing power and the dyeings obtained therefrom have high brilliance and purity of chromatic shades and improved fastness to Washing.

CROSS REFERENCES TO RELATED APPLICATIONS This application is a division of copending application Ser. No. 536,144, filed Mar. 21, 1966, now US. Pat. No. 3,527,747, entitled Reactive Azo Dyestuffs Containing a Tolylsulfonylmethylene Oxytriazine Group.

BACKGROUND OF THE INVENTION (1) Field of the invention The present invention relates to a new class of reactive dyestuffs. More particularly, the present invention relates to dyestuffs which are capable of forming chemical bonds with the hydroxyl groups of cellulose during the dyeing process, thereby giving dyeings which are particularly stable to wet treatments.

(2) Description of the prior art SUMMARY OF THE INVENTION T he present invention provides a new class of dyestuffs characterized by the presence, as a reactive group, of the radical 3,663,541 Patented May 16, 1972 wherein Ar is a substituted or unsubstituted aromatic radical such as an alkyl substituted, preferably lower alkyl substituted, aromatic radical and most preferably and Y is chlorine or bromine. The present invention also provides methods for preparing such dyestuffs.

DESCRIPTION OF THE PREFERRED EMBODIMENTS These dyestuffs may be represented by the following general formula:

wherein n is an integer from 1 to 4, Y and Ar are as defined above, and chromogen is the residue of an anthraquinone dyestuff.

The reactive radical (I) contains a mobile halogen which, when bound to a dyestuff residue, can, under suitable conditions, react with the hydroxyl groups of cellulose, with the NH groups of protein fibers or with the NH groups of synthetic polyamides to form covalent bonds between the dyestuff and the fiber.

The halogen, which remains bonded to the triazine nucleus of radical (I), has a markedly higher reactivity as compared to the halogen present in corresponding triazine derivatives which have bonded to the triazine nucleus, instead of the group -OCH SO Ar, other substituents, for example, an amino group, a monoor di-al-kyl substituted amino group, an aralkyl group, a heterocyclic group, an al'koxy group, an aryloxy group, a thioalkyl group or a thioaryl group.

On the other hand, the reactivity of the triazine nucleus is slightly reduced because of the presence of the group OCH -SO Ar, thus resulting in greater stability during drying and storage.

The higher reactivity of the dyestuffs of the present invention, which contain the radical (I) as a reactive group, as compared to the dyestuffs containing, as reactive groups, the radical (II) \NJ X (11 wherein X is NH NHR, OH, OR, SH or SR, R being a substituted or unsubstituted alkyl or aryl group, can be shown by the fact that the reactive dyestuffs containing the radical (I) are capable of dyeing cellulose fibers from an alkaline bath at 40 C., Whereas the reactive dyestuffs containing the radical (II) require higher bath temperatures, such as for instance 85 C. This remarkably improved reactivity also allows the use of lower concentrations of alkalies, as well as the use of continuous dyeing methods, thus reducing the cost of dyeing.

Besides the high reactivity, the dyestuffs of the present invention have numerous additional advantages, such as very good dyeing power, high brilliance and purity of the chromatic shade, and improved fastness to wet treatments of dyed or printed cellulose materials and natural or synthetic polyamide materials.

The dyestuffs of the present invention may be prepared by reacting cyanuric chloride (III) with an aryl-sulfonyl carbinol (IV) and thereafter condensing the thus obtained triazine (V) with an anthraquinone containing a free amino group to yield the reactive dyestuff (VI).

' Ar-SOr-CIL-OH h/ N N c1 L J-or 01% j-p-onrsolflu (III) (V) anthraqulnone containing a free amino group N lV-NlI-f To! wherein R is the residue of the anthraquinone dyestutf used.

In order to improve the storage stability of the dyestuffs of the present invention to buffering substances such as borates, phosphates, or monosodium phosphate, disodium phosphate or mixtures thereof may be added thereto.

The present invention also provides cellulose and natural or synthetic materials dyed or printed with one or more of the dyestuffs containing, as a reactive group, the radical (I).

The following examples serve to further illustrate the present invention without in any way limiting the scope thereof.

EXAMPLE 1 Preparation of the triazine (VII) A solution of 0.1 mol of p-tolyl-hydroxymethyl-sulfone in 100 ml. of acetone was introduced dropwise within 20- 30 minutes, while maintaining the temperature at about G, into a solution of 0.1 mol of cyanuric chloride in 200 ml. of acetone. Then, within about 40 minutes, a solution of 0.1 mol of collidine in 50 ml. of acetone was introduced, while the temperature was maintained at about 0 C. The collidine hydrochloride immediately began to precipitate. The mixture was kept under agitation at 0 for 5 hours and then the collidine hydrochloride was filtered off. The acetone solution filtrate was poured into water and ice under agitation. The precipitated product was collected by filtration and dried under vacuum. After crystallization from carbon tetrachloride, it had a melting point of 16870 C.

EXAMPLE 2 0.01 mol of the triazine (VII) (prepared as described in Example 1) was dissolved in m1. of acetone and the solution was added dropwise at 20 C. under agitation to an aqueous solution containing 0.01 mol of 1-amino-2- sulfo-4-(4-amino-3-sulfoanilino)-anthraquinone and 0.01 mol of sodium acetate. After completion of the addition, the agitation was continued until complete solution occurred. Then the solution was neutralized and the dyestuff salted out. The dyestnlf, which was collected by filtration, had the following structure:

l O] I slO Na 1 N l l 0 NH -NH- \N o-orn-smQ-on;

It gave a very fast blue dyeing when applied to cellulose fibers.

Variations and modifications can, of course, be made without departing from the spirit and scope of the invention.

Having thus described the invention, what is desired to be secured by Letters Patent and is hereby claimed is:

1. A reactive dyestulf of the formula:

0 |L NH2 (1 l kSOaNa so N C I 3 a ll NH N Q 0 NII-C N N=(IJ 2. A reactive dyestutf of having the structure:

m some s o N-u. 11 .1 lH-NH. N :l

OCH2-SO2C1I3 References Cited UNITED STATES PATENTS 3,073,824 1/1963 Gunstet al 260249 3,095,415 6/1963 Staeuble et al. 260249 3,499,896 3/1970 Neetf 260249 JOHN M. FORD, Primary Examiner U.S. Cl. X.R.

22 3 I UNITED STATES PATENT OFFICE CERTIFICATE OF CO'RREC'HDN PatentNo'. 3,663,541 Dated May 16, 1972 ANGELO MANGINI, ANTONIO TUNDO, BIANCA FLAVIA Inventofls) BONINI and MARTA ROSETTI It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

. Column 1, in the first structural formula, lines 20-25, that portion of the formula reading;

should read N Column 4, line 54: dyestuff of having" should read dyestuff having Signed and sealed this lhth day of November 1972.,

(SEAL) Attest:

AglJ:l;gi.FgE%gI-ER,JR. ROBERT GOTTSCHALK g oer I Commissioner of Patents 

